JP6975972B2 - Method for manufacturing YF3 film-forming body - Google Patents

Description

The present invention relates to a _{method for producing a YF 3} film-forming body.

For example, halogen-based corrosive gases such as fluorine and chlorine, which are highly reactive, are often used as plasma sources in etching steps, CVD deposition steps, resist removing ashing steps, etc. in semiconductor manufacturing processes. In order to prevent corrosion of manufacturing equipment by plasma, high plasma resistance is required for the members directly exposed to the corrosive gas and plasma. Currently, in order to ensure plasma resistance in the semiconductor manufacturing device, by depositing a film of yttria on the surface of the production device (Y 2 _{O 3)} is performed. For example, Patent Document 1 discloses a technique for forming an Itria film on the surface of a film-deposited object by sputtering.

Japanese Unexamined Patent Publication No. 2009-287058

By the way, when it reacts with a fluorine-based gas, it mainly produces _{YF 3. At that time, there is a problem that the YF 3} formed on the surface of the film-deposited body is detached and the film-deposited body is consumed, and the detached particles are mixed in the product to deteriorate the quality of the semiconductor product. _{Therefore, a technique for forming a YF 3} film, which is more resistant to plasma than Yttrium, on the surface of the film to be formed is expected. However, it is technically difficult to form a YF ₃ film of thick high purity on the surface of the deposition target object. Therefore, at present, a _{YF 3 film formation body in which a YF 3 film thinner than the required film thickness or a YF 3} film having a low purity due to containing other compounds is formed on the surface of the film formation body. Is manufactured.

Therefore, the present invention provides a method for producing _{a YF 3 film-forming body capable of producing a YF 3} film-forming body in which a thick and high-purity YF ₃ film is formed on the surface of the film-deposited body. The purpose.

The present invention includes an evaporation step of evaporating _{YF 3 in} an atmosphere of an inert gas, an acceleration step of accelerating the inert gas containing _{YF 3 evaporated in the evaporation step so as to become a supersonic gas flow, and acceleration. It is a method for manufacturing a YF 3} film-forming body including a film-forming step of ejecting a gas flow accelerated in the step onto _{a film-deposited body to form a YF 3} film on the surface of the film-deposited body.

According to this configuration, the evaporation step evaporates the YF _{3 in} the atmosphere of the inert gas, and the acceleration step causes the _{inert gas containing the YF 3} evaporated in the evaporation step to become a supersonic gas flow. By the film forming step, the gas flow accelerated in the accelerating step is ejected to the film-deposited _{object, and a YF 3 film is formed on the surface of the film-deposited object. This makes it possible to manufacture a YF 3} film-forming body in which a thick and high-purity YF ₃ film is formed on the surface of the film-deposited body.

According to the manufacturing method of the YF ₃ deposited film of the present invention can be thick and high purity YF ₃ of the membrane to produce a YF ₃ deposited film formed on the surface of the deposition material.

It is a figure which shows the SFJ-PVD apparatus which concerns on embodiment. It is a table which shows the film thickness of the YF _{3 film-forming body of an experimental example. (A) is a diagram showing the YF 3} film of sample number 8 of the experimental example _{, (B) is a diagram showing the YF 3} film of sample number 17 of the experimental example, and (C) is a diagram showing the sample number 18 of the experimental example. It is a figure which shows the YF _{3 film of.} It is a table which shows the crystallite size of the YF _{3 film formation body of an experimental example.} It is a graph which shows the result of the X-ray crystal structure analysis of an experimental example. It is a graph which shows the result of the X-ray crystal structure analysis of an experimental example. It is a graph which shows the result of the X-ray crystal structure analysis of an experimental example. It is a graph which shows the result of the X-ray crystal structure analysis of an experimental example. It is a graph which shows the result of the X-ray crystal structure analysis of an experimental example.

_{Hereinafter, a method for producing a YF 3} film-forming body according to an embodiment of the present invention will be described. _{In the present embodiment, a film of YF 3} is formed on the surface of the film to be filmed by Supersonic Free Jet (SFJ) physical vapor deposition (PVD). Supersonic free jet physical vapor deposition is performed by the SFJ-PVD apparatus described below.

As shown in FIG. 1, the SFJ-PVD apparatus 1 includes _{an evaporation chamber 2 for evaporating YF 3} which is a film forming material, and a film forming chamber 3 which is a vacuum chamber for film forming. The evaporation chamber 2 and the film forming chamber 3 are connected by a transfer pipe 4. _{Inert gas such as He, Ar, N 2} is supplied to the evaporative chamber 2 from the gas supply source 7 via the valve 5 and the mass flow controller 6 at a predetermined flow rate, and the inside of the evaporative chamber 2 has a predetermined pressure. The atmosphere is an inert gas. Since the atmosphere of He has the fastest sound velocity, it is preferable that the gas supply source 7 supplies He gas to the evaporation chamber 2.

Inside the evaporation chamber 2, a water-cooled and horizontally movable XY stage 8 is installed. _{The YF 3} material 9 which is a film forming material is placed on the XY stage 8. The YF ₃ material 9 is irradiated with, for example, an Nd: YAG laser having a wavelength of about λ = 532 nm from the laser source 15 via the quartz window 10, the lens 11, and the mirrors 12, 13, and 14. The laser output of the laser source 15 is measured by the power meter 16. The lens 11 can move the distance Z from the position closest to the _{YF 3} material 9 shown by the solid line in FIG. 1 to the position farthest from the _{YF 3 material 9 shown by the broken line in FIG.} By moving the _{lens 11, the distance between the YF 3} material 9 and the lens 11 can be changed as appropriate.

On the other hand, the rotary pump 18 and the mechanical booster pump 19 are connected to the film forming chamber 3 via a valve 17. The inside of the film forming chamber 3 is exhausted by the operation of the rotary pump 18 and the mechanical booster pump 19, and an ultra-high vacuum atmosphere of about ^{10-10 Torr is created.} Inside the film forming chamber 3, an XYZ stage 20 is provided so that the holder 21 can be moved in the horizontal direction and the vertical direction. The holder 21 has an electrical resistance heating system. The film-forming object 22 for film formation is fixed to the holder 21. The other end of the transfer pipe 4 connected to the evaporation chamber 2 is guided to the inside of the film forming chamber 3, and the supersonic nozzle 23 is attached to the tip of the transfer pipe 4. The supersonic nozzle 23 is heated by the nozzle heater 24.

_{Hereinafter, a method for manufacturing a YF 3} film-forming body using the SFJ-PVD apparatus 1 will be described. In the evaporation chamber, an evaporation step is performed in which the _{YF 3} material 9 is evaporated by the Nd: YAG laser from the laser source 15 in the atmosphere of He gas, which is an inert gas supplied from the gas supply source 7. _{The YF 3} material 9 is heated and evaporated by the Nd: YAG laser from the laser source 15, and fine particles having a diameter on the order of nanometers are formed from the atoms evaporated from _{the YF 3 material 9.}

An acceleration step is performed in which the He gas, which is an inert gas containing _{YF 3} evaporated in the evaporation step, is accelerated so as to have a supersonic gas flow. A gas flow is generated between the evaporation chamber 2 and the film forming chamber 3 due to the pressure difference, and _{the fine particles of YF 3} generated in the evaporation chamber 2 pass through the transfer tube 4 together with the atmosphere gas He gas in the film forming chamber. Transferred to 3. The _{fluid containing the fine particles of YF 3} and He gas is accelerated by the supersonic nozzle 23 into a supersonic gas flow (air flow of a supersonic free jet).

A film forming step is performed in which the gas flow accelerated in the accelerating step is ejected onto _{the film-deposited body 22 to form a film of YF 3 on the surface of the film-deposited body 22.} The _{fluid containing the fine particles of YF 3} and He gas is ejected from the supersonic nozzle 23 toward the film-deposited body 22 in the film forming chamber 3 as a supersonic gas flow. _{The fine particles of YF 3} contained in the He gas are deposited (physically vapor-deposited) on the film-deposited object 22 to be deposited. As described above, YF ₃ film is formed consisting of particles of YF ₃ on the HiNarumakutai 22.

_{In the present embodiment, the YF 3} material 9 is evaporated in the atmosphere of the inert gas in the evaporation chamber 2 of the SFJ-PVD device 1 by the evaporation step, and the supersonic nozzle 23 of the SFJ-PVD device 1 is subjected to the acceleration step. _{The inert gas containing YF 3} evaporated in the evaporation step is accelerated so as to become a supersonic gas flow, and the gas flow accelerated in the acceleration step in the film forming chamber 3 by the film forming step is the supersonic nozzle 23. A film of YF ₃ is formed on the surface of the film-deposited body 22. This makes it possible to manufacture _{a YF 3} film-forming body in which a thick and high-purity YF ₃ film is formed on the surface of the film-deposited body 22.

Although the embodiment of the present invention has been described above, the present invention is not limited to the above embodiment and is carried out in various forms. _{For example, Ar or N 2} can be applied in addition to He as the inert gas having an atmosphere that evaporates _{YF 3} in the evaporation step. Further, a heat source other than the laser may be applied as the heat source for evaporating _{YF 3} in the evaporation step.

(Experimental example)

By forming a film of YF ₃ on the surface of the substrate is a deposition target object 22 under the conditions shown in FIG. 2 with the SFJ-PVD apparatus 1 shown in FIG. 1, YF ₃ deposited film was produced. First, the film thickness of the YF ₃ film 30 YF ₃ Narumakutai produced was measured. FIG. 2 is a table showing the film thickness _{of the YF 3 film-forming body of the experimental example.} In FIG. 2, the pressure means the pressure inside the evaporation chamber 2.

Further, the distance Z is 174mm 2, a 174mm distance Z from the position closest to the YF ₃ material 9 shown in solid lines in the figure 1, YF ₃ the lens 11 is indicated by broken lines in the figure 1 It means that it is arranged at the position farthest from the material 9. When this distance Z is 174 mm, the distance between the YF ₃ material 9 and the lens 11 is 440 mm, which is the focal length of the lens 11.

Further, the distance Z is 87mm in Fig. 2, a 87mm distance Z from the position closest to the YF ₃ material 9 shown in solid lines in the figure 1, YF ₃ the lens 11 is indicated by broken lines in the figure 1 means that are arranged from the farthest position from the timber 9 to 174 mm-87 mm = 87 mm by approaching the YF ₃ material 9 position. When this distance Z is 87 mm, the distance between the YF ₃ material 9 and the lens 11 is 87 mm shorter than the focal length of the lens 11 of 440 mm. Therefore, when the distance Z is 87 mm, the irradiation area of the laser is wider than when the distance Z is 174 mm, and the power density of the laser is lowered.

Further, the distance Z is 0mm 2, a 0mm distance Z from the position closest to the YF ₃ material 9 shown in solid lines in the figure 1, YF ₃ the lens 11 is indicated by the solid line in the figure 1 It means that it is arranged at the position closest to the material 9. When this distance Z is 0 mm, the distance between the YF ₃ material 9 and the lens 11 is 174 mm shorter than the focal length of the lens 11 of 440 mm. Therefore, when the distance Z is 0 mm, the irradiation area of the laser is wider than when the distance Z is 87 mm, and the power density of the laser is lowered.

The substrate type in FIG. 2 conforms to Japanese Industrial Standards (JIS). The film thickness in FIG. 2 is _{the average value of the length measurement values at five points in the cross-sectional photograph of the manufactured YF 3} film-forming sample by a scanning electron microscope (SEM), and is expressed up to the first decimal place. Has been done. _{The YF 3} film formations of sample numbers 4, 5 and 18 are manufactured under the same laser power, pressure and distance Z conditions. _{The YF 3} film formations of sample numbers 12 and 17 are manufactured under the same laser output, pressure and distance Z conditions.

As shown in FIG. 2 and FIG. ₃ (A), YF 3 film 30 having a thickness of 8.0μm on the deposited film 22 of the sample No. 8 was formed. As shown in FIG. 2 and FIG. 3 (B), the deposited film 22 of the sample No. 17 YF ₃ film 30 of large thickness of 284.0μm was formed. As shown in FIGS. 2 and 3 (C), a YF ₃ film 30 having a thicker film thickness of 616.6 μm was formed on the film-formed object 22 of sample No. 17. The pattern extending diagonally to the lower left and right of _{the YF 3} film 30 in FIG. 3C is a processing scratch when processing the sample.

The composition of the YF ₃ Narumakutai of YF ₃ film 30 was then produced was analyzed. FIG. 4 is a table showing the crystallite size _{of the YF 3 film-forming body of the experimental example.} In FIG. 4, the 5-point average crystallite size of each sample is arranged in order from the top. Sample numbers 19 to 21 are samples whose film thickness has not been measured. 5, FIG. 6, FIG. 7, FIG. 8 and FIG. 9 are graphs showing the results of X-ray crystal structure analysis of experimental examples. In FIGS. 5 to 9, the broken line _{indicates the peak where the YF 3} target and the JCPDS (Joint Committeeon Powder Diffraction Standards) card (01-070-1935) coincide.

As shown in FIGS. 5-9, the peak of all samples are consistent with the peak of YF ₃ target and JCPDS card. This means that the YF ₃ film 30 of each sample is composed of _{pure YF 3} containing no other compounds or the like. As a result of this experiment is to provide a method of producing a YF ₃ deposited film of the present invention, thick and high purity YF ₃ of the membrane to produce a YF ₃ deposited film formed on the surface of the deposition target object It shows that it can be done.

1 ... SFJ-PVD device, 2 ... Evaporation chamber, 3 ... Film formation chamber, 4 ... Transfer pipe, 5 ... Valve, 6 ... Mass flow controller, 7 ... Gas supply source, 8 ... XY stage, 9 ... YF ₃ materials 10, ... Quartz window, 11 ... Lens, 12, 13, 14 ... Mirror, 15 ... Laser source, 16 ... Power meter, 17 ... Bulb, 18 ... Rotary pump, 19 ... Mechanical booster pump, 20 ... XYZ Stage, 21 ... holder, 22 ... film object, 23 ... supersonic nozzle, 24 ... nozzle heater, 30 ... YF ₃ film, Z ... distance.

Claims (1)

The evaporation process that evaporates _{YF 3 in} the atmosphere of the inert gas,
An acceleration step of accelerating the inert gas containing _{YF 3} evaporated in the evaporation step so as to have a supersonic gas flow.
A film forming step of ejecting the gas flow accelerated in the accelerating step onto the film to be formed to form a _{YF 3 film on the surface of the film to be formed.}
A method for manufacturing a YF ₃ film-forming body.

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